[(2R,3S,4S,5R)-3,4,5,6-tetraacetyloxyoxan-2-yl]methyl acetate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: According to scheme XIV, the coupling of penta-O-acetyl-D-galactopyranose (36 g, 92 mmoles) with p-cresol (30 g, 280 mmoles) is carried out by fusion in the presence of anhydrous ZnCl2 (1.8 g) at 160° C. for 30 minutes, according Helferich technique. After cooling, a chromatography on a column of 60H silica (solvent:hexane-ethyl acetate: 90/10-v/v) is directly performed on the mixture and gives 15 g, yield=40% of 4-methylphenyl 2,3,4,6-tetra-O-acetyl-α-D-galactopyranoside, which crystallises in ethanol. Its analytical characteristics are identical as the one described before. After cooling

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 8.9 g of p-cresol, 8.9 g of penta-O-acetyl-D-galactopyranose and 0.56 g of ZnCl2 are mixed, heated to 160° C. and kept at this temperature for 30 minutes, according to HELFERICH's method. After cooling to 60° C., the reaction medium is taken up with 400 ml of CH2Cl2 and washed with twice 400 ml of water and then with a solution of sodium hydroxide (≈1N) until the aqueous phase is practically colourless. The organic phase is finally washed with twice 400 ml of water, dried over anhydrous sodium sulfate and then evaporated to dryness in a water bath (temperature: 35°-40° C.) to give a residue of 7.08 g (yield=70%). Chromatography on a column of 60H silica (solvent: hexane/ethyl acetate: 90/10 v/v) gives 2.9 g of the compound 1 (yield=29%) and 1.17 g of its β anomer (yield=12%). After cooling to 60° C. washed with twice 400 ml of water The organic phase is finally washed with twice 400 ml of water dried over anhydrous sodium sulfate evaporated to dryness in a water bath (temperature: 35°-40° C.) to give a residue of 7.08 g (yield=70%)

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 8.9 g of p-cresol, 8.9 g of penta-O-acetyl-D-galactopyranose and 0.56 g of ZnCl2 are mixed, heated to 160° C. and kept at this temperature for 30 minutes, according to HELFERICH's method. After cooling to 60° C., the reaction medium is taken up with 400 ml of CH2Cl2 and washed with twice 400 ml of water and then with a solution of sodium hydroxide (≈1N) until the aqueous phase is practically colourless. The organic phase is finally washed with twice 400 ml of water, dried over anhydrous sodium sulfate and then evaporated to dryness in a water bath (temperature: 35°-40° C.) to give a residue of 7.08 g (yield=70%). Chromatography on a column of 60H silica (solvent: hexane/ethyl acetate: 90/10 v/v) gives 2.9 g of the compound 1 (yield=29%) and 1.17 g of its β anomer (yield=12%). After cooling to 60° C. washed with twice 400 ml of water The organic phase is finally washed with twice 400 ml of water dried over anhydrous sodium sulfate evaporated to dryness in a water bath (temperature: 35°-40° C.) to give a residue of 7.08 g (yield=70%)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: BF3.Et2O (8.5 mL, 67.0 mmol) was added dropwise to a solution of of 1,2,3,4,6-penta-O-acetyl-α,β-D-galactose (5e) (See FIG. 7) (5.1 g, 13.1 mmol) and Br(CH2)2OH (1.15 mL, 16.2 mmol) in CH2Cl2 (24 mL) at 0° C. under N2. After 1 hour, the solution was warmed to room temperature. After 24 hours, the reaction solution was added to ice water (20 mL) and extracted with CH2Cl2 (30 mL×3). These extracts were combined, washed with water (20 mL), sat. NaHCO3 (aq., 20 mL), water (20 mL), dried (MgSO4), filt Vögtle ered, and the solvent removed. The residue purified by flash chromatography (EtOAc:hexane, 1:3) to give 2-bromoethyl 2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside (4j) (See FIG. 7) (4.01 g, 67%) as a white solid; mp 116-117° C. (EtOAc/hexane) [lit., (Coles et al., J. Am. Chem. Soc., 60:1020-1022 (1938), which is hereby incorporated by reference) 111° C.; lit., (Dahmén et al., “2-Bromoethyl Glycosides—Synthesis and Characterization,” Carbohydr. Res., 116:303-307 (1983), which is hereby incorporated by reference) 114-116° C. (EtOAc/light pet. ether)]; [α]27D=−3.8 (c 0.81, CHCl3) [lit., (Dahmén et al., “2-Bromoethyl Glycosides—Synthesis and Characterization,” Carbohydr. Res., 116:303-307 (1983), which is hereby incorporated by reference) [a]23D=−5 (c 1.4, CDCl3)]; 1H NMR (200 MHz, CDCl3) δ 1.98, 2.05, 2.08, 2.15 (s×4, 3H×4, Ac×4), 3.43-3.50 (m, 2H), 3.75-3.95 (m, 2H), 4.12-4.24 (m, 3H), 4.53 (d, J1,2 8 Hz, 1H, H-1), 5.02 (dd, J2,3 11 Hz, J2,3 3 Hz, 1H, H-3), 5.23 (dd, J1,2 8 Hz, J2,3 11 Hz, 1H, H-2), 5.40 (br d, J3,4 3 Hz, 1H, H-4). NaSSO2CH3 (85 mg, 0.63 mmol) was added to a solution of 4j (See FIG. 7) (223 mg, 0.49 mmol) in DMF (6 mL) under N2 and warmed to 55° C. After 30 hours, the solution was cooled and the solvent removed. The residue was purified by flash chromatography (EtOAc:hexane, 1:1) to give 1j (See FIG. 7) (198 mg, 83%) as a white foam; [α]27D=+9.1 (c 1.41. CHCl3); IR (film) 1747 cm−1 (C═O), 1320, 1133 cm−1 (S—SO2); 1H NMR (500 MHz, CDCl3) δ 1.98, 2.05, 2.09, 2.15 (s×4, 3H×4, Ac×4), 3.35 (s, 3H, CH3SO2—), 3.35-3.38 (m, 2H, —CH2S—), 3.84 (ddd, J 6.1 Hz, J 7.1 Hz, J 10.5 Hz, 1H, —OCHH′—), 3.92 (td, J4,5 1.1 Hz, Jt 6.6 Hz, 1H, H-5), 4.10-4.21 (m, 3H, H-6, H-6′, —OCHH′—), 4.52 (d, J1,2 8.0 Hz, 1H, H-1), 5.01 (dd, J2,3 10.3 Hz, J3,4 3.5 Hz, 1H, H-3),5.20 (dd, J1,2 8.0 Hz, J2,3 10.3 Hz, 1H, H-2), 5.40 (dd, J3,4 3.5 Hz, J4,5 1.1 Hz, 1H, H-4); 13C NMR (100 MHz, CDCl3) δ 20.6,20.7, 20.8 (CH3COO—×4), 36.1, (—CH2S—), 50.6 (CH3SO2—), 61.2 (—OCH2—), 67.0, 68.3, 68.5, 70.8, 71.0 (C-2, C-3, C-4, C-5, C-6), 101.3 (C-1), 169.5, 170.0, 170.1, 170.4 (CH3COO—×4); HRMS m/z (FAB+): Found 487.0936 (M+H+); C17H27O12S2 requires 487.0944. After 24 hours extracted with CH2Cl2 (30 mL×3) washed with water (20 mL), sat. NaHCO3 (aq., 20 mL), water (20 mL) dried (MgSO4) the solvent removed The residue purified by flash chromatography (EtOAc:hexane, 1:3)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1,2,3,4,6-penta-O-acetyl-galactopyranose (1.17 g, 3 mmol) was dissolved in dry CH2Cl2 (15 ml), then trimethylsilyl azide (416 mg, 3.6 mmol) and SnCl4 (0.18 ml) were added under nitrogen. The mixture was stirred at room temperature for 24 hours. The reaction mixture was subsequently diluted with CH2Cl2 (40 ml), dried over MgSo4 and evaporated. The residue was purified by chromatography using hexane/EtOAc 8:7 v/v as the mobile phase to give 2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl azide (1.05 g, 94%). dried over MgSo4 evaporated The residue was purified by chromatography

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: BF3.Et2O (8.5 mL, 67.0 mmol) was added dropwise to a solution of of 1,2,3,4,6-penta-O-acetyl-α,β-D-galactose (5e) (See FIG. 7) (5.1 g, 13.1 mmol) and Br(CH2)2OH (1.15 mL, 16.2 mmol) in CH2Cl2 (24 mL) at 0° C. under N2. After 1 hour, the solution was warmed to room temperature. After 24 hours, the reaction solution was added to ice water (20 mL) and extracted with CH2Cl2 (30 mL×3). These extracts were combined, washed with water (20 mL), sat. NaHCO3 (aq., 20 mL), water (20 mL), dried (MgSO4), filt Vogtle ered, and the solvent removed. The residue purified by flash chromatography (EtOAc:hexane, 1:3) to give 2-bromoethyl 2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside (4j) (See FIG. 7) (4.01 g, 67%) as a white solid; mp 116-117° C. (EtOAc/hexane) [lit., (Coles et al., J. Am. Chem. Soc., 60:1020-1022 (1938), which is hereby incorporated by reference) 111° C.; lit., (Dahmén et al., “2-Bromoethyl Glycosides—Synthesis and Characterization,” Carbohydr. Res., 116:303-307 (1983), which is hereby incorporated by reference) 114-116° C. (EtOAc/light pet. ether)]; [α]27D=−3.8 (c 0.81, CHCl3) [lit., (Dahmén et al., “2-Bromoethyl Glycosides—Synthesis and Characterization,” Carbohydr. Res., 116:303-307 (1983), which is hereby incorporated by reference) [α]23D=−5 (c 1.4, CDCl3)]; 1H NMR (200 MHz, CDCl3) δ 1.98, 2.05, 2.08, 2.15 (s×4, 3H×4, Ac×4), 3.43-3.50 (m, 2H), 3.75-3.95 (m, 2H), 4.12-4.24 (m, 3H), 4.53 (d, J1,2 8 Hz, 1H, H-1), 5.02 (dd, J2,3 11 Hz, J3,4 3 Hz, 1H, H-3), 5.23 (dd, J1,2 8 Hz, J2,3 11 Hz, 1H, H-2), 5.40 (br d, J3,4 3 Hz, 1H, H-4). NaSSO2CH3 (85 mg, 0.63 mmol) was added to a solution of 4j (See FIG. 7) (223 mg, 0.49 mmol) in DMF (6 mL) under N2 and warmed to 55° C. After 30 hours, the solution was cooled and the solvent removed. The residue was purified by flash chromatography (EtOAc:hexane, 1:1) to give 1j (See FIG. 7) (198 mg, 83%) as a white foam; [α]27D=+9.1 (c 1.41, CHCl3); IR (film) 1747 cm−1 (C═O), 1320, 1133 cm−1 (S—SO2); 1H NMR (500 MHz, CDCl3) δ 1.98, 2.05, 2.09, 2.15 (s×4, 3H×4, Ac×4), 3.35 (s, 3H, CH3SO2—), 3.35-3.38 (m, 2H, —CH2S—), 3.84 (ddd, J 6.1 Hz, J 7.1 Hz, J 10.5 Hz, 1H, —OCHH′—), 3.92 (td, J4,5 1.1 Hz, Jt 6.6 Hz, 1H, H-5), 4.10-4.21 (m, 3H, H-6, H-6′, —OCHH′—), 4.52 (d, J1,2 8.0 Hz, 1H, H-1), 5.01 (dd, J2,3 10.3 Hz, J3,4 3.5 Hz, 1H, H-3), 5.20 (dd, J1,2 8.0 Hz, J2,3 10.3 Hz, 1H, H-2), 5.40 (dd, J3 4 3.5 Hz, J4,5 1.1 Hz, 1H, H-4); 13C NMR (100 MHz, CDCl3) δ 20.6, 20.7, 20.8 (CH3COO—×4), 36.1, (—CH2S—), 50.6 (CH3SO2—), 61.2 (—OCH2—). 67.0, 68.3, 68.5, 70.8, 71.0 (C-2, C-3, C-4, C-5, C-6), 101.3 (C-1), 169.5, 170.0, 170.1, 170.4 (CH3COO—×4); HRMS m/z (FAB+): Found 487.0936 (M+H+); C17H27O12S2 requires 487.0944. After 24 hours extracted with CH2Cl2 (30 mL×3) washed with water (20 mL), sat. NaHCO3 (aq., 20 mL), water (20 mL) dried (MgSO4) the solvent removed The residue purified by flash chromatography (EtOAc:hexane, 1:3)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1,2,3,4,6-penta-O-acetyl-galactopyranose (1.17 g, 3 mmol) was dissolved in dry CH2Cl2 (15 ml), then trimethylsilyl azide (416 mg, 3.6 mmol) and SnCl4 (0.18 ml) were added under nitrogen. The mixture was stirred at room temperature for 24 hours. The reaction mixture was subsequently diluted with CH2Cl2 (40 ml), dried over MgSO4 and evaporated. The residue was purified by chromatography using hexane/EtOAc 8:7 v/v as the mobile phase to give 2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl azide (1.05 g, 94%). dried over MgSO4 evaporated The residue was purified by chromatography

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: According to scheme XIV, the coupling of penta-O-acetyl-D-galactopyranose (36 g, 92 mmoles) with p-cresol (30 g, 280 mmoles) is carried out by fusion in the presence of anhydrous ZnCl2 (1.8 g) at 160° C. for 30 minutes, according Helferich technique. After cooling, a chromatography on a column of 60H silica (solvent:hexane-ethyl acetate: 90/10-v/v) is directly performed on the mixture and gives 15 g, yield=40% of 4-methylphenyl 2,3,4,6-tetra-O-acetyl-α-D-galactopyranoside, which crystallises in ethanol. Its analytical characteristics are identical as the one described before. After cooling

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 8.9 g of p-cresol, 8.9 g of penta-O-acetyl-D-galactopyranose and 0.56 g of ZnCl2 are mixed, heated to 160° C. and kept at this temperature for 30 minutes, according to HELFERICH's method. After cooling to 60° C., the reaction medium is taken up with 400 ml of CH2Cl2 and washed with twice 400 ml of water and then with a solution of sodium hydroxide (≈1N) until the aqueous phase is practically colourless. The organic phase is finally washed with twice 400 ml of water, dried over anhydrous sodium sulfate and then evaporated to dryness in a water bath (temperature: 35°-40° C.) to give a residue of 7.08 g (yield=70%). Chromatography on a column of 60H silica (solvent: hexane/ethyl acetate: 90/10 v/v) gives 2.9 g of the compound 1 (yield=29%) and 1.17 g of its β anomer (yield=12%). After cooling to 60° C. washed with twice 400 ml of water The organic phase is finally washed with twice 400 ml of water dried over anhydrous sodium sulfate evaporated to dryness in a water bath (temperature: 35°-40° C.) to give a residue of 7.08 g (yield=70%)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: BF3.Et2O (8.5 mL, 67.0 mmol) was added dropwise to a solution of of 1,2,3,4,6-penta-O-acetyl-α,β-D-galactose (5e) (See FIG. 7) (5.1 g, 13.1 mmol) and Br(CH2)2OH (1.15 mL, 16.2 mmol) in CH2Cl2 (24 mL) at 0° C. under N2. After 1 hour, the solution was warmed to room temperature. After 24 hours, the reaction solution was added to ice water (20 mL) and extracted with CH2Cl2 (30 mL×3). These extracts were combined, washed with water (20 mL), sat. NaHCO3 (aq., 20 mL), water (20 mL), dried (MgSO4), filt Vögtle ered, and the solvent removed. The residue purified by flash chromatography (EtOAc:hexane, 1:3) to give 2-bromoethyl 2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside (4j) (See FIG. 7) (4.01 g, 67%) as a white solid; mp 116-117° C. (EtOAc/hexane) [lit., (Coles et al., J. Am. Chem. Soc., 60:1020-1022 (1938), which is hereby incorporated by reference) 111° C.; lit., (Dahmén et al., “2-Bromoethyl Glycosides—Synthesis and Characterization,” Carbohydr. Res., 116:303-307 (1983), which is hereby incorporated by reference) 114-116° C. (EtOAc/light pet. ether)]; [α]27D=−3.8 (c 0.81, CHCl3) [lit., (Dahmén et al., “2-Bromoethyl Glycosides—Synthesis and Characterization,” Carbohydr. Res., 116:303-307 (1983), which is hereby incorporated by reference) [a]23D=−5 (c 1.4, CDCl3)]; 1H NMR (200 MHz, CDCl3) δ 1.98, 2.05, 2.08, 2.15 (s×4, 3H×4, Ac×4), 3.43-3.50 (m, 2H), 3.75-3.95 (m, 2H), 4.12-4.24 (m, 3H), 4.53 (d, J1,2 8 Hz, 1H, H-1), 5.02 (dd, J2,3 11 Hz, J2,3 3 Hz, 1H, H-3), 5.23 (dd, J1,2 8 Hz, J2,3 11 Hz, 1H, H-2), 5.40 (br d, J3,4 3 Hz, 1H, H-4). NaSSO2CH3 (85 mg, 0.63 mmol) was added to a solution of 4j (See FIG. 7) (223 mg, 0.49 mmol) in DMF (6 mL) under N2 and warmed to 55° C. After 30 hours, the solution was cooled and the solvent removed. The residue was purified by flash chromatography (EtOAc:hexane, 1:1) to give 1j (See FIG. 7) (198 mg, 83%) as a white foam; [α]27D=+9.1 (c 1.41. CHCl3); IR (film) 1747 cm−1 (C═O), 1320, 1133 cm−1 (S—SO2); 1H NMR (500 MHz, CDCl3) δ 1.98, 2.05, 2.09, 2.15 (s×4, 3H×4, Ac×4), 3.35 (s, 3H, CH3SO2—), 3.35-3.38 (m, 2H, —CH2S—), 3.84 (ddd, J 6.1 Hz, J 7.1 Hz, J 10.5 Hz, 1H, —OCHH′—), 3.92 (td, J4,5 1.1 Hz, Jt 6.6 Hz, 1H, H-5), 4.10-4.21 (m, 3H, H-6, H-6′, —OCHH′—), 4.52 (d, J1,2 8.0 Hz, 1H, H-1), 5.01 (dd, J2,3 10.3 Hz, J3,4 3.5 Hz, 1H, H-3),5.20 (dd, J1,2 8.0 Hz, J2,3 10.3 Hz, 1H, H-2), 5.40 (dd, J3,4 3.5 Hz, J4,5 1.1 Hz, 1H, H-4); 13C NMR (100 MHz, CDCl3) δ 20.6,20.7, 20.8 (CH3COO—×4), 36.1, (—CH2S—), 50.6 (CH3SO2—), 61.2 (—OCH2—), 67.0, 68.3, 68.5, 70.8, 71.0 (C-2, C-3, C-4, C-5, C-6), 101.3 (C-1), 169.5, 170.0, 170.1, 170.4 (CH3COO—×4); HRMS m/z (FAB+): Found 487.0936 (M+H+); C17H27O12S2 requires 487.0944. After 24 hours extracted with CH2Cl2 (30 mL×3) washed with water (20 mL), sat. NaHCO3 (aq., 20 mL), water (20 mL) dried (MgSO4) the solvent removed The residue purified by flash chromatography (EtOAc:hexane, 1:3)